Diesel additive, preparation method and usage method thereof

ABSTRACT

The present invention relates to a diesel additive. The diesel additive comprises 80-100 wt. % of a nonylphenol polyether amine and 0-20 wt. % of a diluent, based on the total weight of the diesel additive. The diesel additive provided by the present invention can be used to remove carbon deposits at the nozzle of a diesel engine.

FIELD OF THE INVENTION

The present disclosure relates to a diesel additive, in particular, to the diesel additive which can be used to remove carbon deposits at the nozzle of a diesel engine.

BACKGROUND OF THE INVENTION

There are many catalytic cracked components and a high content of unsaturated hydrocarbon impurities in diesel ingredients, so carbon deposition easily forms at the nozzle of the engine which affects she normal operation of the engine, resulting in increased fuel consumption, deteriorated exhaust emission, and shortened engine life.

CN1986751A1 discloses a diesel additive comprising polyether amine, polyisobutylene succinimide, boronated ashless dispersant and the like.

U.S. Pat. No. 4,484,357 discloses a dye composition for preventing the carbon deposition at the nozzle of un-direct injection diesel vehicle, and its composition is succinimide, alkyl amine, and metal deactivator. U.S. Pat. No. 5,313,534 discloses a detergent using aliphatic amine and aliphatic amide to reduce the pollution of the diesel engine nozzle and the comprised aliphatic amine and aliphatic amide are straight chain alkyl groups.

U.S. Pat. No. 5,752,989 discloses a composition comprising: a major proportion of compression ignition dye and a minor proportion of additive, and the additive comprises a dispersant and a carrying oil, wherein the dispersant comprises at least one ingredient of succinimides and polyalkyl amine, and the carrying oil comprises various kinds of polyethers.

U.S. Pat. No. 8,915,976 B1 discloses a composition for increasing the fuel efficiency of the diesel, which comprises: tribenzyl phosphate ester (TCP), nonylphenyl polyether amine and glycol ether solution. The composition can effectively improve the emissions and reduce the fuel consumption.

SUMMARY OF THE INVENTION

The present disclosure provides a diesel additive used to remove the carbon deposits at the nozzle of the diesel engine.

Certain aspects of the present disclosure provide a diesel additive, which comprises 80-100 wt. % of a nonylphenol polyether amine and 0-20 wt. % of a diluent, based on the total weight of the diesel additive.

Certain aspects of the present disclosure provide a method for preparing the diesel additive, which comprises the step of mixing the ingredients of the diesel additive.

Certain aspects of the present disclosure provide a method for using the diesel additive, which comprises the step of adding the diesel additive to diesel.

The diesel additive provided by the present disclosure has good diesel nozzle carbon deposit cleaning performance.

DETAILED DESCRIPTION

It should be understood that without departing from the scope or spirit of the present disclosure, the person skilled in the art can conceive other various embodiments according to the teachings of this specification and can modify them. Therefore, the following specific embodiments are not in a limiting sense.

Unless otherwise indicated, all numbers used in this specification and claims for expressing the sizes, quantities and physicochemical properties of features should be understood as in all cases to be modified by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters listed in the foregoing specification and attached claims are all approximations, and thee person skilled in the art can use the teachings disclosed herein to appropriately change these approximations for seeking the desired properties. The use of numerical range represented by endpoints comprises all numbers within that range and any sub-range within that range, e.g., 1 in 5 comprises 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4 and 5, and so on.

Diesel Additive

According to certain specific embodiments, the diesel additive provided by the present disclosure comprises 80-100 wt. % of a nonylphenol polyether amine and 0-20 wt. % of a diluent, based on the total weight of the diesel additive.

Nonylphenol Polyether Amine

In the diesel additive, the nonylphenol polyether amine contributes to remove the carbon deposits of the diesel engine (for example, the carbon deposits at the nozzle of the diesel engine). The polar amine group in the nonylphenol polyether amine can be adsorbed to the metal surface of the diesel engine, while the structure of nonylphenol is relatively similar to the structure of carbon deposits, so the carbon deposits attached to the metal surface (for example, the back side of the gas intake valve) of the diesel engine can be stripped down and dispersed into small particles, which can then be burned off in the combustion chamber.

According to the prior art, the industry generally believes that polyether amines may be used in gasoline additive to remove the carbon deposits of the gasoline engine, but it is difficult to be used in diesel additive to clean the carbon deposits of the diesel engine, because: (1) the work form of the diesel engine is significantly different from that of the gasoline engine, and the pressure and temperature in the diesel engine are much higher than those in the gasoline engine; (2) the compositions of the diesel and the gasoline are quite different, and with respect to the gasoline engine nozzle, the carbon deposits of the diesel engine nozzle is formed at a higher temperature and is harder to remove, so the cleaning effect of polyether amines for the carbon deposits of the diesel engine nozzle is not obvious; (3) the stability of polyether amines is relatively poor, and it is easy to decompose at high temperatures, which also leads to the polyether amines are difficult to be applied in the diesel additive.

The inventor of the present disclosure surprisingly found that some nonylphenol polyether amines can be used in the diesel additive, which have a good cleaning performance for the carbon deposits of the diesel engine nozzle. The nonylphenol polyether amines comprise the following general formula:

Wherein, m=2, n=24-26, y=1-2.

According to certain specific embodiments, the polyether amine has a molecular weight of 1700-3500.

According to certain specific embodiments, the polyether amine is present at a level of 80-100 wt. % based on the total weight of the diesel additive. When the polyether amine is present at a level of less than 80 wt. %, the diesel additive may have the problem of a declined removal efficiency of the carbon deposits at nozzle.

Diluent

In the diesel additive, the diluent contributes to reduce the viscosity of the diesel additive. According to certain specific embodiments, the diluent may comprise: at least one of the saturated straight-chain hydrocarbon solvents, cycloalkanes solvents, and mixed aromatic hydrocarbon agents.

According to certain specific embodiments, the diluent is present at a level of 0-20 wt. % based on the total weight of the diesel additive.

The Method for Preparing the Diesel Additive

According to certain specific embodiments, the ingredients of the diesel additive can be mixed together to obtain the diesel additive. The description about each ingredient of the diesel additive can be found in the “Diesel Additive” section of the present description.

According to certain specific embodiments, the ingredients used to prepare the diesel additive can be added to a stainless steel vessel and mixed under the conditions of normal temperature (about 25° C.) and normal pressure (about 1 atm) to obtain the diesel additive.

The Method for Using the Diesel Additive

According to certain specific embodiments, the diesel additive according to the present disclosure can be added into diesel. According to certain specific embodiments, under the conditions of normal temperature (about 25° C.) and normal pressure (about 1 atm), the diesel additive can be added to the diesel in the proportion of 1:1000-1:2000. The description about the diesel additive can be found in the “Diesel Additive” section of the present description.

According to certain specific embodiments, the fuel comprises diesel. According to certain specific embodiments, the diesel comprises, at least one of the 0# diesel and −10# diesel.

The following specific embodiments are intended to describe the present disclosure illustratively rather than restrictively.

Specific embodiment 1 is a diesel additive, which comprises 80-100 wt. % of the polyether amine and 0-20 wt. % of the diluent, based on the total weight of the diesel additive.

Specific embodiment 2 is the diesel additive according to the Specific embodiment 1, wherein, the nonylphenol polyether amine comprises the following general formula:

wherein, m=2, n=24-26, y=1-2.

Specific embodiment 3 is the diesel additive according to the Specific embodiment 1 or the Specific embodiment 2, wherein, the nonylphenol polyether amine has a molecular weight of 1700-3500.

Specific embodiment 4 is the diesel additive according to any one of the Specific embodiments 1 to 3, wherein the nonylphenol poiyether amine is present at a level of 90-100 wt. %

Specific embodiment 5 is the diesel additive according to am one of the Specific embodiments 1 to 4, wherein the diluent comprises: at least one of a saturated straight-chain hydrocarbon solvent, a cycloalkanes solvent, and a mixed aromatic hydrocarbon agent.

Specific embodiment 6 is the diesel additive according to any one of the Specific embodiments 1 to 5, wherein the diluent is present at a level of 0-20 wt. %.

Specific embodiment is a method for preparing the diesel additive according to any one of the Specific embodiments 1 to 6, which comprises the step of mixing the ingredients of the diesel additive.

Specific embodiment 8 is a method for using the diesel additive according to any one of the Specific embodiments 1 to 7, which comprises the step of adding the diesel additive into diesel.

Specific embodiment 9 is the method according 10 the Specific embodiment 8, wherein the fuel is diesel.

The following Examples are used to further illustrate the present disclosure, but the scope of the present disclosure should not be understood as being limited to the following specific Examples.

EXAMPLES

The names, functions, chemical names and manufacturers of the main materials used to formulate the diesel additives of the present disclosure are lifted in the following table 1a.

TABLE 1a Physical and chemical Name Component characteristic Manufacturer FL-1000 Nonylphenol polyether Molecular weight is Huntsman Chemical Trading amine about 1000 Company PEA-L Nonylphenol polyether Molecular weight is Qingyuanxing Chemical amine about 1700 Technology Co. Ltd. PEA-PEO Nonylphenol polyether Molecular weight is Huntsman Chemical Trading amine about 2000 Company PEA-H Nonylphenol polyether Molecular weight is Qingyuanxing Chemical amine about 3500 Technology Co. Ltd. D60 Saturated straight-chain Straight-chain Exxon Mobil Company hydrocarbon solvent hydrocarbon solvent oil with the flash point of about 60° C.

Preparation of the Diesel Additives

Under the conditions of normal tempera Hire (about 25° C.) and normal pressure (about 1 atm), the ingredients of the diesel additive were added to a stainless steel container and mixed to obtain the diesel additive.

Adding the Diesel Additive to Diesel

Under the conditions of normal temperature (about 25° C.) and normal pressure (about 1 atm), the diesel additive was added to the fuel (for example, diesel) in the proportion of 1:1000.

Carbon Deposit Removal Performance Test of the Diesel Additives

In the present disclosure, “diesel engine nozzle carbon deposit removal rate test” was used to measure the capability of the diesel additives provided by the present disclosure to remove carbon deposits at the nozzle of the diesel engine. When the carbon deposit removal rate was measured to be greater than 50%, it indicated that the tested diesel additive had a good ability to remove the carbon deposits at the nozzle of fuel engine.

The test reagents and test equipment involved in “diesel engine nozzle carbon deposit removal rate test” are listed in the following table 1b.

TABLE 1b Test reagent and test equipment Manufacturer N-heptane (AR) Sinopharm Chemical Reagent Co., Ltd. Petroleum ether (AR) Jiangsu Yonghua Fine Chemicals Co., Ltd. Anhydrous ethanol (AR) Sinopharm Chemical Reagent Co., Ltd. High efficiency engine carbon deposit Lanzhou Victory Petrochemical Company removal agents original liquid Cyclopentadiene Lanzhou Victory Petrochemical Company Base diesel (0# diesel) China Petroleum and National Gas Co., Ltd L-3 Automobile diesel cleaning performance Lanzhou Victory Petrochemical Company test machine Balance (accurate to 0.1 mg) Mettler Toledo Instruments (Shanghai) Co., Ltd. Dryer (with color changing silica Lanzhou Victory Petrochemical Company geldesiccant) Oven (with temperature controlled at Thermo Fisher Science and Technology 100 ± 2° C.) (China) Co., Ltd. Micro-injector (accurate to 1 ml) Lanzhou Victory Petrochemical Company Metal sample cup Lanzhou Victory Petrochemical Company Metal spoon Lanzhou Victory Petrochemical Company Aid (cyclopentadiene) Lanzhou Victory Petrochemical Company Volumetric flask (300 ml) Lanzhou Victory Petrochemical Company Thermometer (accurate to 0.1° C.) Lanzhou Victory Petrochemical Company

Diesel Engine Nozzle Carbon Deposit Removal Rate Test

1. Preparation of the Deposit Collector

1.1 The carbon deposit collector (an aluminium plate with 10 cm length and 8 cm width) was soaked in anhydrous ethanol for 60 minutes, until its surface was bright and had no stains. Then the carbon deposit collector was cleaned by running water and soaked in anhydrous ethanol for 5 minutes, then picked up with tweezers and placed into a an oven, at 100° C. to dry for not less than 15 minutes.

1.2 The carbon deposit collector was removed from the oven and placed into a desiccator to cool to room temperature (about 25° C.).

1.3 After the carbon deposit collector was cooled, the temperature of it was measured with a thermometer and recorded. The mass of the carbon deposit collector was recorded and the carbon deposit collector was placed into the a desiccator to get ready to be used (As noted, it should be ensured that in this step, the temperature change of the carbon deposit collector between two consecutive weighing was not more than 0.2° C., and the weighing error was less than 0.2 mg).

2. Preparation of Instrument (L-3 Diesel Cleaning Performance Test Machine)

2.1 Metering Pump Calibration

2.1.1 20 mL base diesel was poured into a 50 mL beaker.

2.1.2 “Power” switch and “Start” switch of the instrument were pressed down, the plastic card on pump head of the instrument was pressed down to squeeze the hose, the plastic wrench in the upper right corner was pulled up two buckles (pulled up twice), and then the oil feeding pipe was plugged into the container filled with oil sample;

2.1.3 The metal connecting tube which connects with the hose at the outlet of the metering pump was unplugged, and a 10 mL graduated cylinder was put at the outlet of the oil pipe;

2.1.4 When the metering pump was used initially, hose and hose clamp were moved its position forward or backward or the hose was replaced by a new one, the pump speed was set to 5.6 rev/min, the “Oil supply mode” switch was pulled to the “supply oil” position, and when the oil began to drop out from the oil pipe outlet, the stopwatch was pressed down to start timing, the time for dropping full of 10 mL diesel was measured and the time should be within the range of 8 minutes and 40 seconds to 8 minutes and 55 seconds. If the time was not within this range, the speed of the pump can be adjusted, and the above steps were carried out again until the calibration was achieved;

2.1.5 The unplugged oil pipe to its original was restored.

2.2 The fuel supply system was cleaned

2.2.1 20 mL washed diesel or automobile diesel without additives were poured into a container, an oil feeding pipe was inserted, and the top cover of the L-3 diesel cleaning performance test machine was opened, the slider driving the oil pipe was lifted up to move to the left side of the transmission bracket platform and a 50 mL beaker was placed beneath the oil outlet pipe;

2.2.2 When the “supply oil mode” switch was in the “stop” position, the “full speed” switch of the pump was pressed down, and the fuel supply system was cleaned until the reagent was pumped over;

2.2.3 20 mL n-heptane was poured into the container, and steps 2.2.1 to 2.2.2 were repeated;

2.2.4 20 mL oil samples to be tested were poured into the container, and steps 2.2.1 to 2.2.2 were repeated.

3. Preparation of the Oil Sample

3.1 Preparation of the Oil sample

100 mL oil sample to be tested was taken and poured into a metal sample cup, a certain amount of aid was drawn off with micro-injector and pushed into a metal spoon, 1 ML toluene (or xylene) was added and stirred for 30 laps, and then was poured into the oil sample to be tested and stirred for 1 minute. The cup lid was covered, and the oil feeding pipe of the L-3 diesel cleaning performance test machine was inserted.

3.2 Base diesel sample preparation

100 ml base diesel was taken and poured into the metal sample cup. The mixed aids were poured into the base diesel sample and stirred for 1 minute by using the aids formulation method in the step 3.1. The cup lid was covered, and the oil feeding pipe was inserted.

3.3 Preparation of the diesel sample adding with the diesel additive

100 ml base diesel was taken and poured into the metal sample cup. The diesel additive provided by the present disclosure was added into the diesel according to the volume ratio and stirred well. The mixed aids were poured into the oil sample and stirred 1 minute by using the aids formulation method in the step 3.1. The cup lid was covered, and the oil feeding pipe was inserted.

4. Coking Test (the Test is Carried Out By Using the Base Diesel Sample)

4.1 The test timer of the L-3 diesel cleaning performance test machine was set to 90 min;

4.2 The top lid of the test cover of the L-3 diesel cleaning performance test machine was opened and the deposit collector was put on the top of the heater. The clamping mechanisms at both ends of the heater were pulled up, and the pressing slice was turned to compact the both sides of the deposit collector, and then a temperature thermocouple was inserted. The inclined plane of the waste oil box was coated with a layer of silicone grease, then placed under the collector and kept consistent with the inclined plane on the lower edge of the collector;

4.3 The “power” switch, “start” switch, and “heating” switch of the L-3 diesel cleaning performance test machine were successively pressed down and the heater began to heat, so that the temperature of the deposit collector reached to the set temperature (250° C.);

4.4 The oil output pipe of L-3 diesel cleaning performance test machine was pointed to the 50 ml beaker, and the “oil supply mode” switch was in the “stop” position. The “full speed” switch of the pump was pressed down to pump the oil, and when the oil output pipe began to drip oil, the “full speed” switch was immediately pressed down to stop oil feeding. When the temperature of the collector reached to the set temperature, the slider (the slider is a removable metal block on L-3 diesel cleaning performance test machine, through which the oil tubes can be communicated and the reciprocating injection of the diesel can be simulated) was inserted to the dowel pin on the transmission bracket platform, and the oil output pipe was placed on the deposit collector;

4.5 The “reciprocating proceeding” switch on the instrument panel was pressed down and the “oil supply mode” switch was pulled up to the “timing oil supply”. Supplying oil to collector began and the lest timing started, and the top lid of the test cover was closed.

4.6 The flow of the pump, reciprocating proceeding state and the temperature of the deposit collector were maintained. When reaching the count time, the pump, reciprocating proceeding and the heating power were shut off automatically and the test was finished which was showed by the sound and light of the “test finished” alarm;

4.7 The “power” switch, “reciprocating proceeding”switch, and “heating” switch were restored to the close state;

4.8 The temperature thermocouple of the deposit collector was drawn out and the waste oil box was taken out. The slider (the slider was a removable metal block on L-3 diesel cleaning performance test machine, through which the oil tubes can be communicated and the reciprocating injection of the diesel can be simulated) was lifted up and moved to the left side of the transmission bracket platform. The oil output pipe was placed above a 50 ml beaker, and the clamping mechanism of the heater was loosened, and then the deposit collector was removed with forceps;

4.9 Silicone grease was firstly wiped off the backside of the cooled deposit collector with a paper towel, and then the cooled deposit collector was placed in a beaker filled with n-heptane, soaked for 1 min and then removed out.

4.10 The deposit collector was soaked into a breaker filled with petroleum ether and taken out after 1 min.

4.11 The paper stick formed by rolling the paper was inserted into the thermometer hole of the deposit collector to absorb the agent in the hole;

4.12 The deposit collector was weighed;

4.13 After the test was finished, the pipeline was cleaned according to the steps in the 2.2 “Clean the fuel supply system” section, and then metering was performed.

5. Carbon Deposit Removal Experiment (Using the Diesel Sample Added with Diesel Additive)

The experiment was carried out by repeating the steps of 4.1 to 4.13, except that the diesel sample added with diesel additive was used.

6. Result Calculation

6.1 The calculation formula for the formation amount of the diesel deposits

m=m1−m0   (formula 1)

In the formula:

m represents the mass of the carbon deposits generated during the test, and the unit is mg;

m₁ represents the final mass of the carbon deposit collector in the test, and the unit is mg;

m₀ represents the initial mass of the carbon deposit collector in the test, and the unit is mg.

6.2 The calculation formula of the diesel nozzle carbon deposit removal rate

δ=[(m−m ₂]×100%  (formula 2)

In the formula:

δ represents the carbon deposit removal rate of the diesel engine nozzle, and the unit is %:

m represents the mass of the carbon deposits generated by the diesel during the test, and the unit is mg:

m₂ represents the final mass of the carbon deposit collector in the test, and the unit is mg.

Examples 1 to 5

According to the method described above and on the base of the formulation listed in Table 2 (the values listed in Table 2 are all based on weight percentage), under the conditions of normal temperature (25 ° C.) and normal pressure (about 1 atm), the ingredients of the diesel additive are added to a stainless steel container and mixed to obtain the diesel-additives 1 to 5.

According to the method described above, the diesel engine nozzle carbon deposit removal rates of the diesel additives 1 to 5 are tested and the results are listed in Table 4.

TABLE 2 1 2 3 4 5 PEA-PEO 100 90 80 0 0 PEA-L 0 0 0 100 0 PEA-H 0 0 0 0 100 Diluent 0 10 20 0 0 Total 100 100 100 100 100

Comparative Examples C1 to C6

According to the method described above and on the base of the formulation listed in Table 3 (the values listed in Table 3 are all based on weight percentage), under the conditions of normal temperature (25° C.) and normal pressure (about 1 atm), the ingredients of the diesel additive are added to a stainless steel container and mixed to obtain the diesel additives C1 to C6.

According to the method described above, the diesel engine nozzle carbon deposit removal rates of the diesel additives C1 to C6 are tested and the results are listed in Table 4.

TABLE 3 C1 C2 C3 C4 C5 PEA-PEO 75 0 0 0 0 FL-1000 0 100 0 0 0 Diluent 25 0 0 0 0 LZ9049 0 0 100 0 0 nonylbenzene 0 polyether amine 0 0 0 100 (US) nonylbenzene 100 polyether amine 0 0 0 0 (NJ) Total 100 100 100 100 100

TABLE 4 Carbon deposit cleaning rate (%) Example 1 72.4 Example 2 67.2 Example 3 56.3 Example 4 51.3 Example 5 62.3 Comparative Example 1 47.8 Comparative Example 2 48.6 Comparative Example 3 43.3 Comparative Example 4 12.6 Comparative Example 5 5.6 Comparative Example 6 −66.7 (Blank Example) The negative value represents, relative to its mass before the test, the final mass of the carbon deposit collector is increased during the test)

According to the Examples 1-5 and Comparative Examples C1-C6, the diesel additives provided by the present disclosure have a good nozzle carbon deposit cleaning rate.

According to Example 1 and Example 2, when the nonylphenol polyether amine in diesel additives is present at a level of 90-100%, the diesel additives provided by the present disclosure have a particularly good nozzle carbon deposit cleaning rate.

According to Example 1, Example 4 and Example 5, when the nonylphenol polyether amine in the diesel additives has a molecular weight of 1700-3500, the diesel additives provided by the present disclosure have a particularly good nozzle carbon deposit cleaning rate.

In summary, the diesel additives provided by the present disclosure have good nozzle carbon deposit cleaning performance.

Although for purposes of illustration, the specific embodiments described above contain many specific details, but the ordinary skilled person in the art will appreciate that many variations, modifications, substitutions and changes of such details all fall into the scope of the present disclosure which is protected by the claims. Therefore, the disclosure described in the specific embodiments does not make any restriction to the present disclosure which is protected by the claims. The appropriate scope of the present disclosure should be defined by the claims and the appropriate legal equivalents. All cited references are incorporated herein by reference in its entirety. 

1. A diesel additive, comprising: 80-100 wt. % of a nonylphenol polyether amine; and 0-20 wt. % of a diluent, based on the total weight of the diesel additive.
 2. The diesel additive according to claim 1, wherein the nonylphenol polyether amine comprises the following general formula:

wherein, m=2, n=24-26, y=1-2.
 3. The diesel additive according to claim 1, wherein the nonylphenol polyether amine has a molecular weight of 1700-3500.
 4. The diesel additive according to claim 1, wherein the nonylphenol polyether amine is present at a level of 90-100 wt. %.
 5. The diesel additive according to claim 1, wherein the diluent comprises: at least one of a saturated straight-chain hydrocarbon solvent, a cycloalkanes solvent, and a mixed aromatic hydrocarbon agent.
 6. The diesel additive according to claim 1, wherein the diluent is present at a level of 0-20 wt. %.
 7. A method for preparing the diesel additive according to claim 1, comprising the step of mixing the ingredients of the diesel additive.
 8. A method for using the diesel additive according to claim 1, comprising the step of adding the diesel additive to diesel.
 9. The diesel additive according to claim 5, wherein the diluent is present at a level of 0-20 wt. %. 